NMR study of the electric field gradient in the paramagnetic phase of M<Subscript>3</Subscript>V<Subscript>2</Subscript>O<Subscript>8</Subscript> (M = Co,Ni) compounds

The NMR spectra and the decay of a spin echo signal from ⁵¹V nuclei in Kagome-staircase Co₃V₂O₈ (CVO) and Ni₃V₂O₈ (NVO) single crystals are measured in the temperature range 30–300 K and a magnetic field H ₀ = 20 kOe. The orientation dependences of the ⁵¹V NMR line shape are used to determine the electric field gradient (EFG) parameters, namely, quadrupole frequency ν _Q and asymmetry parameter η. These parameters for NVO and CVO are ν _Q = 180(10) kHz, η = 0.5(1) and ν _Q = 130(10) kHz, η = 0.6(1), respectively. A comparison of the results of calculating EFG tensors with a point charge model and the NMR data indicates that the crystallographically equivalent vanadium atoms in the Ni₃V₂O₈ and Co₃V₂O₈ compounds differ in the EFG axis orientation. M₃V₂O₈ crystals are found to have vanadium positions (V1, V2) with different orientations of the z axis, which specifies the direction of the principal value of EFG (V _zz ): these orientations lie in the bc plane and make an angle of either +51(5)° (V1) or −51(5)° (V2) with axis c. In the temperature range 30–300 K, the EFG tensor components and the local symmetry of the charge surrounding of the vanadium positions in NVO and CVO oxides are found to change insignificantly.     

Electric quadrupole interactions in Ru-Sc alloys

In TDPAC studies of the electric quadrupole interaction in Ru_xSc_1–x alloys two different electric fieldgradients (EFG) have been observed at the site of⁹⁹Ru: V_zz(I)=12.6·10¹⁷ V/cm² and V_zz(II)=18.9·10₁₇ V/cm². The corresponding relative fractions f(I) and f(II), respectively, vary with the Ru concentration x. For low concentrations x<0.01 most nuclei (f(I)0.8) experience the smaller EFG V_zz(I). At x=0.01, however, the fraction f(I) goes abruptly to zero and V_zz(II) becomes dominant. In view of these results the previous interpretation of V_zz(II) as the EFG of dilute Ru on substitutional Sc sites can no longer be maintained. The Ru-Sc configurations producing these EFG's have not yet been identified. In the intermetallic compound Ru₂Sc the interaction is completely different, in RuSc₃, however, similar values have been observed.     

Study of the electric quadrupole interaction at Ta impurities in rare earth metal hosts

The time differential perturbed angular correlation technique has been used to measure the electric fieldgradient (EFG) at the site of¹⁸¹Ta impurities in the heavy Rare Earth metals Gd, Tb, Dy, Ho and Er at room temperature. It is found that the ratio α ≡ ¦V _zz ^eff /V _zz ^lat ¦ between the measured EFGV _zz ^eff and the lattice EFGV _zz ^lat , which is known from lattice sum calculations, is in the order of α?300, suggesting that an important contribution to the EFG is due to electrons localized at the impurity. The ratio α is not constant throughout the Rare Earth series. It decreases from Gd to Tb and increases between Tb and Er. This behaviour is compared to the results of a previous investigation with the impurity Cd in the same hosts.     

A Theoretical Study of <Superscript>51</Superscript>V Electric Field Gradient Tensors in Pyrovanadates and Metavanadates

A computational study of the ⁵¹V electric field gradient (EFG) tensors in pyrovanadates, α-Zn₂V₂O₇, Cd₂V₂O₇, β-Mg₂V₂O₇ and BaCaV₂O₇, and the metavanadates, LiVO₃, α-NaVO₃, KVO₃, ZnV₂O₆ and MgV₂O₆, is presented. Restricted Hartree–Fock and hybrid density functional theory calculations have been used to investigate the effects of the size of vanadium-oxygen clusters, basis set size, proton-termination and embedded cluster techniques on the accuracy of the calculated EFG tensors. Good agreement between theory and experiment is obtained for most of the vanadates. A sound methodology is suggested for calculating the EFG tensor in pyrovanadates which contain isolated V₂O₇ ⁴⁻ clusters. For metavanadates, the charges of the bridging oxygen atoms can be differentiated from those of terminal oxygen atoms by terminating the former with hydrogen atoms, and embedded cluster molecular orbital calculations are useful in accounting for the long-range electrostatic interactions which influence the EFG tensor components. EFG tensor orientations vary for different pyrovanadate structural types, and individual components are confined by symmetry elements in the metavanadates. A preliminary comparison is made between ⁵¹V EFG tensors calculated with ab initio and plane wave methods. Theoretical EFG tensor components and orientations, in combination with experimental ⁵¹V solid-state nuclear magnetic resonance data, are demonstrated to be useful tools for prediction of molecular structure. Authors' address: Robert W. Schurko, Department of Chemistry and Biochemistry, University of Windsor, Windsor, Ontario N9B 3P4, Canada     

Solid-state 17O NMR study of the electric-field-gradient and chemical shielding tensors in polycrystalline γ-glycine

We report the first experimental determination of the carboxylate oxygen electric-field-gradient (EFG) and chemical shielding (CS) tensors in polycrystalline γ-glycine. Analysis of magic-angle spinning (MAS) and stationary ¹⁷O NMR spectra of [¹⁷O]-γ-glycine obtained at 9.4, 14.1, 16.4, and 18.8 T yields the magnitudes of the ¹⁷O EFG and CS tensors and the relative orientations between the two tensors. Extensive quantum chemical calculations at both the restricted Hartree–Fock and density functional levels have been performed to present the absolute tensor orientations in term of the molecular frame. We have demonstrated that ¹⁷O NMR tensor information could be unambiguously derived by the multiple field analyses of stationary ¹⁷O NMR spectra.     

The local structure of Cs(I) and Cs(II) in a Cs2ZnCl4 single crystal studied by nuclear magnetic resonance

The rotation patterns of the ¹³³Cs (I=7/2) nuclear magnetic resonance (NMR) in a Cs₂ZnCl₄ single crystal grown by using the slow evaporation method were measured in two mutually perpendicular crystal planes. Two different groups of Cs resonances were recorded; this result points to the existence of two types of crystallographically inequivalent Cs(I) and Cs(II). The angular dependences of the NMR spectra led to different values for the quadrupole coupling constants and asymmetry parameters: e²qQ/h=148 kHz and η=0.11 for the Cs(I) ion, and e²qQ/h=274 kHz and η=0.66 for the Cs(II) ion. The EFG tensors of Cs(I) and Cs(II) are asymmetric, and the orientations of the principal axes of the EFG tensors do not coincide. Only, the principal Y-axes of the EFG tensors coincide for the Cs(I) and Cs(II) sites. The Cs(I) ion is surrounded by 11 chlorine ions, making it rather free and high in symmetry. The Cs(II) ion has only nine neighbors and seems to be more tight than the Cs(I) ion.     

Determination of the orientation of the electric field gradient at the Cu(1) site from the Mössbauer spectra of textured pellets made of YBa2Cu3O7−δ superconductor

A textured pellet of YBa₂Cu₃O_7?δ was prepared and doped with⁵⁷Co. After subsequent heat treatments the cobalt was found at the two copper sites. The degree of alignment of individual crystallites (about 40%) was determined from the Mössbauer spectrum by using a method developed by the authors [1]. The same method showed that the most characteristic doublet component of such spectra (δ=0.08 mm/s; |ΔE _Q|=1.96 mm/s) is associated with a site, most probably a Cu(1) site, where the EFG is parallel to thec direction of the unit cell. The sign ofV _zz turned out to be negative, giving a negative quadrupole splitting (ΔE _Q=?1.96 mm/s) for that component.     

Static electric quadrupole interaction of Ta- and Hf-ions in barium and lead titanate

The static electric quadrupole interaction of¹⁸¹Ta and¹⁷⁸Hf in polycrystalline barium and lead titanate at the site of titanium has been measured using time differential PAC and the Mössbauer effect. The electric field gradients (EFG) at room temperature at the¹⁸¹Ta nucleus are ¦V _zz¦=(3.6±0.2)·10¹⁷V/cm² in BaTiO₃ and ¦V _zz¦=(14.6±0.6)·10¹⁷ V/cm² in PbTiO₃. The temperature dependence of the quadrupole interaction has been studied giving the following EFG values: ¦V _zz¦=(2.4±0.2)·10¹⁷ V/cm² in the monoclinic and ¦V _zz¦=(1.1±0.3)·10¹⁷ V/cm² in the rhomboedral phase of BaTiO₃, and ¦V _zz¦=(15.7±0.6)·10¹⁷ V/cm² for¹⁸¹Ta/PbTiO ₃ at 77 °K. The EFG of¹⁷⁸Hf in PbTiO₃ has been derived from a Mössbauer effect experiment to beV _zz=+(10.7±0.5)·10¹⁷ V/cm². The results are compared with EFG's calculated in a point charge model and with experimental EFG's measured at⁴⁴Sc and⁵⁷Fe in the same titanates by other authors. Contributions of covalent bonds to the effective EFG's in perovskit crystals are discussed.     

Ga and Pt NMR study of UPtGa5

^69,71Ga and ¹⁹⁵Pt NMR/NQR measurements have been carried out for the 5f-antiferromagnet, UPtGa₅. From a NMR study using a single crystal sample, Knight shift measurements are reported for two different Ga sites and for Pt. The principal axes of the electrical field gradient tensor at both Ga sites have been determined and the values of the splitting parameter ν_Q and the asymmetry parameter η have been evaluated. The hyperfine coupling constants with the external field along various directions are also reported for the two Ga sites and Pt.     

The signature of the nuclear quadrupole interaction in continuous phase transitions

A correlation between the largest component of the electric field gradient (EFG) tensor, V_zz, and its asymmetry parameter η is discovered in a series of compounds which exhibt phase transitions. It is shown that all the EFG tensor components depend linearly on a single control parameter. A convenient way to unravel this correlation from V_zz, η-data is presented.     

Magnetic resonance study of arsenic bonding sites in ternary chalcogenide glasses

⁷⁵As NQR and high-field NMR experiments have been performed on Ge_xAs_ySe_1−x−y glasses. Evolution of As bonding structure from arsenic sites with axially symmetric distribution of the electric field gradient (EFG) to highly asymmetric As surroundings has been revealed. Arsenic atoms form pyramidal structural units in Ge₂As₂Se₇ with no evidence of significant concentration of homopolar bonds. In Ge₂As₂Se₅ most of arsenic atoms form structural units with two As-As bonds per atom and asymmetric EFG distribution. Arsenic bondings become more complicated in Ge_0.33As_0.12Se_0.55 where all arsenic sites are highly distorted. The combination of NQR and NMR data provide valuable information on arsenic bonding dynamics in these glasses.     

NMR spin echoes and quadrupole effects in nickel single crystals

NMR spin echo measurements of naturally abundant⁶¹Ni have been performed with Néel-type nickel single crystals at 4.2 K. The NMR excitation condition could properly be chosen in order to get signals either from nuclei situated within magnetic domains or within domain walls. In both cases a quadrupole splitting of the NMR line could be observed. By applying an external magnetic field, the direction of the domain magnetization could be varied with respect to the fcc crystal lattice. From the variation of the quadrupole splitting with the crystallographic direction, the tensor of the electric field gradient (EFG) has been derived. The quadrupole splittings and the corresponding field gradients in the principal axis system of the EFG are: Δv_Q kHz, Δv_Q kHz, Δv_Q kHz, V_<111>=(6.6±0.5)·10¹⁸ V/m², V_<110>=4.6±0.5)·10¹⁸ V/m², V_<112>=(2.0±0.5)·10¹⁸ V/m².     

Mössbauer effect study of SrEu2Fe2O7

The antiferromagnetic ferrite SrEu₂Fe₂O₇ was studied by Mössbauer effect of⁵⁷Fe in the range 77–650 K. Analysis of the data gives a Neel temperature of 544 K±2 K and an extrapolated effective magnetic fieldH(OK) of 545 kG. Good fit to the spectrum at 290 K is obtained withH _eff=475 kG, δ=0.37 mm/s, 1/2e ² qQ(1+η ²/3)=0.70mm/s, θ and ?=90°. The Brillouin function forS=5/2 poorly fits the experimental data of hyperfine magnetic fields. In the critical rangeH _eff can be described byH(T)=H(0)D(1?T/T _N )^β, where β nearly 0.29. The quadrupole interaction parameter is quite temperature independent, of the order of 0.69 mm/s in the paramagnetic state. Agreement with the value obtained by a point charge calculation is good. The largest axis of the EFG tensor,V _zz , lies in the plane (110), making an angle of 22.6° with thec axis. The direction of magnetization is nearly perpendicular toV _zz in [110] direction.     

Hyperfine interactions measurements on 181Ta probes in HfV2Hx compounds: (0⩽x≲4)

The electric field gradient (EFG) has been measured on ¹⁸¹Ta probe sites in HfV₂H_x alloys (0?x?4) using the time differential perturbed angular correlation technique. One observes that the main component V_zz of the EFG decreases by a factor of 2 for hydrogen concentrations increasing from x = 0 to x = 4 hydrogen atoms/formula. The opposite behavior was observed on ⁵¹V by using the NMR technique. At T = 4.2 K the EFG tensor is non-axially symmetric. The observed asymmetry factor for x = 0 is η = 0.58(3) and it slightly increases to η = 0.70 for x?4. The system is orthorhombic at low temperatures for all x and the experiments suggest that hydrogen would stabilize a tetragonal phase at higher temperatures. The relaxation effects are absent for x = 0 and vanishingly small for x ? 4 but they are observed at intermediate concentrations supporting the idea of a hydrogen ordering for x = 4.     

Determination of the orientations for the 17O NMR tensors in a polycrystalline l-alanine hydrochloride

We report a solid-state 17O NMR study of the 17O electric-field-gradient (EFG) and chemical shielding (CS) tensors for the carboxyl oxygen in an l-alanine hydrochloride. Using [17O]- and [13C,17O]-L-alanine hydrochlorides, both the magnitudes and the orientations in the molecular frame of the 17O EFG and CS tensors could be determined by the analysis of the 17O magic-angle spinning (MAS) and stationary NMR spectra. For the carbonyl oxygen, the smallest EFG tensor component, V(XX), and the largest EFG component, V(ZZ), roughly lies in the carboxyl molecular plane and the direction of V(XX) is parallel to the dipolar vector between 13C and 17O, that is, the direction of CO bond. The angles between the intermediate EFG component, VYY, and delta33 component, and between delta22 component and VZZ are found to be approximately 10 degrees and 35 degrees , respectively. We also present the results of the quantum chemical calculations for a theoretical hydrogen-bonding model, indicating that hydrogen-bonding strengths make it possible to vary both magnitudes and orientations of the carbonyl 17O EFG tensors in amino acid hydrochlorides.     

Transitions and Spin Dynamics at Very Low Temperature in the Pyrochlores Yb2Ti2O7 and Gd2Sn2O7

An orientational disorder of the cation in [(PyO)D][AuCl₄] crystal was investigated by the ³⁵Cl NQR and ¹H NMR measurements. A structural phase transition was found at ca. 70 K from the temperature dependence of the NQR frequencies both in [(PyO)D][AuCl₄] and [(PyO)H][AuCl₄]. Temperature dependence of the spin-lattice relaxation time T ₁ of the NQR of [AuCl₄]⁻ could be interpreted by an electric field gradient modulation due to the motion of the cation. Characteristics of T ₁ of ³⁵Cl NQR as well as that of ¹H NMR suggest a dynamic orientational disorder of the cation.     

Nuclear acoustic resonance of V51 in a single crystal of V3Si above and below the martensitic transformation

The EFG and the Knight shift anisotropy of V⁵¹ in a single crystal of V³Si have been measured both above and below the martensitic transformation temperature T_m, using the nuclear acoustic resonance technique. Deviations of the axial symmetry of the EFG tensor have been found below T_m. The orientation of the tetragonal c axis in the crystal is also given.